CN1891694A - Method for preparing 1,3-dialkyl-2-imidazolidinone and 1,5- dialkyl-(1,3,5)triazahepane-2,4-diketone - Google Patents
Method for preparing 1,3-dialkyl-2-imidazolidinone and 1,5- dialkyl-(1,3,5)triazahepane-2,4-diketone Download PDFInfo
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Abstract
This method of production is provided by reacting a compound expressed by general formula (1) [wherein, R is >=1 and <=4C alkyl] with a burette in the presence of aprotic polar solvent, passing through a compound expressed by general formula (2) [wherein, R is >=1 and <=4C alkyl] as an intermediate, and obtaining a compound expressed by general formula (3) [wherein, R is >=1 and <=4C alkyl].
Description
Technical field
The present invention relates to 1,3-dialkyl group-2-imidazolone and 1,5-dialkyl group-[1,3,5] three azepans-2, the preparation method of 4-diketone.
Background technology
As existing 1, the preparation method of 3-dialkyl group-2-imidazolone, known have a N, N '-dialkyl group quadrol through the method (with reference to patent documentation 1) of urea cyclisation, through the method (with reference to patent documentation 2) of phosgene cyclisation, through the method (with reference to patent documentation 3) of carbonic acid gas cyclisation, with ethylidene-urea with formalin and the alkylating method of hydrogen reducing (with reference to patent documentation 4) and with the reaction product after 2-imidazolone and the formalin addition with reductive methods (with reference to non-patent literature 1) such as trichoroacetic acid(TCA), formic acid.
In addition, as existing known 1,5-dialkyl group-[1,3,5] three azepans-2, the preparation method of 4-diketone, for example known N that makes, the method for N '-dimethyl-ethylenediamine and azepine propanedioic acid methyl esters reaction and make N, the method of N '-dimethyl-ethylenediamine and ethoxycarbonyl isocyanate reaction (with reference to patent documentation 5) and make N, N '-dimethyl-ethylenediamine and urea reaction generate N, and N '-dimethyl-ethylenediamine two ureas is with the methods (with reference to non-patent literature 2) of its heating under 300 ℃.
In addition, as existing 1, the preparation method of 3-dialkyl group-2-imidazolone, the known N that utilizes, the method that N '-dialkyl group quadrol and urea are prepared.This procedure is simple, is better method, but exists the lower deficiency of yield in existing known method.Afterwards, disclose and improved this insufficient method, this method makes N, N '-dialkyl group quadrol and urea react under the temperature more than 180 ℃ or 180 ℃, and it is reacted under 140 ℃ temperature until generating as 1 of intermediate 1 '-dimethyl-1,1 '-dimethylene, two ureas, under the temperature more than 180 ℃ or 180 ℃, react again, thereby with the preparation of the yield more than 80% or 80% 1,3-dialkyl group-2-imidazolone (with reference to patent documentation 6).
But, if utilize this method, then exist the problem of removing the by product aspect, that is, owing to contain with respect to 1,3-dimethyl-2-imidazolone is the by product 1 of 0.5%～number %, 3-dimethyl-2-alkyl imidazole imine, and the boiling point of this by product and 1,3-dimethyl-2-imidazolone is close, so need very high distillation tower during fractionation by distillation, the treatment process of other method etc. maybe must be arranged.
In addition, contain 1 of above-mentioned by product, 3-dimethyl-2-imidazolone can hinder goal response when using as solvent, as, when using, can block the problem of polymer polymerizing as the preparation solvent of aromatic poly, there is weak point in use.
As suppressing the technology that by product generates, the scheme of record in the patent documentation 7 is disclosed.The document is disclosed 1, and the preparation method of 3-dialkyl group-2-imidazolone adds N continuously for the limit in the aprotic polar solvent that is heated to more than 180 ℃ or 180 ℃, and N '-dialkyl group quadrol and urea limit make its reaction.Control the pair generation that reaction conditions suppresses imines as described above.
[patent documentation 1] spy opens clear 61-236769 communique
[patent documentation 2] spy opens clear 62-181264 communique
[patent documentation 3] spy opens the 2000-026427 communique
[patent documentation 4] spy opens clear 53-98965 communique
[patent documentation 5] Deutsches Reichs-Patent application discloses specification sheets No. 2036172
The 4th, 731, No. 453 specification sheetss of [patent documentation 6] United States Patent (USP)
[patent documentation 7] spy opens flat 10-101651 communique
[non-patent literature 1] Journal of Chemical and Engineering Data, Vol.21, No.2,1976p.150～153
[non-patent literature 2] Journal of the Chemical Society PerkinTransactions 2 (1972-1999), 1981, p.317-319
Summary of the invention
Above-mentioned non-patent literature 2 has been reported from 1,5-dimethyl-[1,3,5] three azepans-2,4-two ketogenesiss 1,3-dimethyl-2-imidazolone.Therefore, expectation 1,5-dialkyl group-[1,3,5] three azepans-2,4-diketone can become and be used to prepare 1, the useful raw material of 3-dialkyl group-2-imidazolone.
The object of the present invention is to provide preparation 1, the novel method of 3-dialkyl group-2-imidazolone.
In addition, the object of the present invention is to provide as 1 of above-mentioned preparation method's reaction intermediate, 5-dialkyl group-[1,3,5] three azepans-2, the novel preparation method of 4-diketone.
The inventor etc. have carried out deep research for solving above-mentioned problem, find that N '-dialkyl group quadrol and urea react in aprotic polar solvent, can access 1 by making N, 3-dialkyl group-2-imidazolone, thus finished the present invention.
In addition, the inventor etc. have carried out deep research for solving above-mentioned problem, find by making N, N '-dialkyl group quadrol and biuret reaction, can access as 1 of above-mentioned reaction intermediate 5-dialkyl group-[1,3,5] three azepans-2, the 4-diketone, thus finished the present invention.
That is, the present invention includes the and the following invention
[1] compound and the biuret of following general formula (1) expression are reacted in the presence of aprotic polar solvent,, obtain the preparation method of the compound of following general formula (3) expression via the compound of representing as the following general formula (2) of intermediate.
(in the formula, R represents that carbonatoms is 1～4 alkyl.)
(in the formula, R represents that carbonatoms is 1～4 alkyl.)
(in the formula, R represents that carbonatoms is 1～4 alkyl.)
[2] make the compound of general formula (1) expression and biuret in the presence of aprotic polar solvent, under 80 ℃～300 ℃ temperature of reaction, react, via following general formula as intermediate
(2) Biao Shi compound obtains the preparation method of the compound of following general formula (3) expression, and the compound of described general formula (1) expression is 1.9～2.1 with respect to the mol ratio of described biuret.
(in the formula, R represents that carbonatoms is 1～4 alkyl.)
(in the formula, R represents that carbonatoms is 1～4 alkyl.)
(in the formula, R represents that carbonatoms is 1～4 alkyl.)
[3] make the compound of following general formula (1) expression and biuret in the presence of aprotic polar solvent, under 80 ℃～300 ℃ temperature of reaction, react, obtain the preparation method of the compound of following general formula (3) expression, the compound of described general formula (1) expression is 1.9～2.1 with respect to the mol ratio of described biuret.
(in the formula, R represents that carbonatoms is 1～4 alkyl.)
(in the formula, R represents that carbonatoms is 1～4 alkyl.)
[4] each preparation method who puts down in writing in [1]～[3], wherein, described aprotic polar solvent is the compound of above-mentioned general formula (3) expression.
[5] compound and the biuret of following general formula (1) expression are reacted under 80 ℃～190 ℃ temperature of reaction, obtain the preparation method of the compound of following general formula (2) expression, the compound of described general formula (1) expression is 0.8～1.2 with respect to the mol ratio of described biuret.
(in the formula, R represents that carbonatoms is 1～4 alkyl.)
(in the formula, R represents that carbonatoms is 1～4 alkyl.)
The invention provides a kind of preparation 1, the novel method of 3-dialkyl group-2-imidazolone.
In addition, the invention provides a kind of preparation 1,5-dialkyl group-[1,3,5] three azepans-2, the novel method of 4-diketone.
Description of drawings
Fig. 1 be embodiment 4 make 1, the gas chromatogram of 3-dialkyl group-2-imidazolone.
Fig. 2 be comparative example 1 make 1, the gas chromatogram of 3-dialkyl group-2-imidazolone.
Embodiment
1 of following general formula (3) expression that the present invention relates to, the preparation method of 3-dialkyl group-2-imidazolone reacts the compound and the biuret of following general formula (1) expression in the presence of aprotic polar solvent.
In above-mentioned general formula (1) and (3), R represents that carbonatoms is 1～4 alkyl.In addition, in the compound of above-mentioned general formula (3) expression, R is identical with the compound of above-mentioned general formula (1) expression of using as raw material.
As the compound of general formula (1) expression, for example can enumerate N, N '-dimethyl-ethylenediamine, N, N '-diethyl ethylenediamine, N, N '-dipropyl quadrol, N, N '-diisopropyl ethylenediamine, N, N '-dibutyl quadrol etc.
The compound of general formula (1) expression can easily obtain by the reaction of ethylene hydrocarbonss such as corresponding monoalkylamine and ethylene dichloride, ethylene dibromide.
Aprotic polar solvent is not particularly limited.As aprotic polar solvent, for example can enumerate N-N-methyl-2-2-pyrrolidone N-, N, N '-dimethyl formamide, N, the compound of N '-N,N-DIMETHYLACETAMIDE, tetramethyl-urea, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, tetramethylene sulfone, diox and above-mentioned general formula (3) expression etc.Wherein, consider that preferred boiling point is the solvent more than 180 ℃ or 180 ℃ from reaction aspect under atmospheric pressure.The compound of above-mentioned general formula (3) expression that described reaction generates, because required and the isolating operation of solvent phase when need not to carry out in reaction, using the solvent that is different from this compound, so preferably.
The usage quantity of aprotic polar solvent is not particularly limited, and usually, with respect to biuret 100 weight parts, its usage quantity is that 20 weight parts or 20 weight parts are above, 1000 weight parts or below 1000 weight parts.
The compound of general formula (1) expression and the usage quantity of biuret are expressed as the compound of general formula (1) expression with the mol ratio on the stoichiometry: biuret=get final product at 2.0: 1.0, mol ratio is preferably 1.9: 1.0 to 2.1: 1.0.If the compound of general formula (1) expression is too small with respect to the ratio of biuret, then yield reduces.If the compound of general formula (1) expression is excessive with respect to the ratio of biuret, need filter biuret when then purifying.Simultaneously also uneconomical.Adopt the usage quantity of above-mentioned scope, can suppress yield and reduce, also do not need to filter biuret when purifying simultaneously, so preferred.
Temperature of reaction is generally 80 ℃～300 ℃.During stepwise reaction, preferably take the method that 2 stages of branch heat, the 1st stage was more than 100 ℃ or 100 ℃, below 190 ℃ or 190 ℃, the 2nd stage was more than 180 ℃ or 180 ℃, below 300 ℃ or 300 ℃, preferred especially the 1st stage is more than 110 ℃ or 110 ℃, below 150 ℃ or 150 ℃, and the 2nd stage was more than 200 ℃ or 200 ℃, below 240 ℃ or 240 ℃.If the temperature in the 1st stage is low excessively, then speed of response reduces, and too high then yield descends.In addition, if the 2nd phase temperature is low excessively, then speed of response and yield all reduce, and the too high pressure vessel etc. that then needs is uneconomical.
Reaction pressure is not particularly limited, and is generally under the normal atmosphere.
The compound of general formula (1) expression and the method for biuret reaction are not particularly limited, can adopt any method in multiple step format, the continous way to implement.
For example, during stepwise reaction, preferably compound that general formula (1) is represented and biuret one-time heating, heat under the temperature more than 180 ℃ or 180 ℃ thereafter below 190 ℃ or 190 ℃ to the decomposition temperature of biuret.The style that has more as the stepwise reaction method, can enumerate following method: with the mixture heating up to 110 of aprotic polar solvent and biuret ℃ or more than 110 ℃, below 150 ℃ or 150 ℃, add the compound of general formula (1) expression, making the compound of general formula (1) expression and the mol ratio of biuret is 1: 1, then be heated to more than 200 ℃ or 200 ℃, below 240 ℃ or 240 ℃, further add the compound of general formula (1) expression, making the compound of general formula (1) expression and the mol ratio of biuret is 2: 1.In addition, the method that also has compound hybrid reaction in reaction vessel that aprotic polar solvent, biuret are represented with whole general formulas (1), at this moment, consider the boiling point of the compound of employed general formula (1) expression, must control reaction temperature remain on more than 180 ℃ or 180 ℃.
During successive reaction, adopt to keep in the aprotic polar solvent of heating in the temperature of reaction, add the compound of general formula (1) expression and the method for biuret continuously in reaction vessel, continuous drawing goes out reaction product.
The compound of the general formula that above-mentioned preparation method obtains (3) expression can reclaim from reaction mixture by operations such as distillations.
In addition, from other viewpoints, the present invention relates to 1 of following general formula (3) expression, the following preparation method of 3-dialkyl group-2-imidazolone.Described preparation method reacts in the presence of aprotic polar solvent for compound and the biuret that makes following general formula (1) expression, via the compound of representing as the following general formula (2) of intermediate, obtains the compound of following general formula (3) expression.
In above-mentioned general formula (1)～(3), R represents that carbonatoms is 1～4 alkyl.In addition, in the compound of above-mentioned general formula (2) and (3) expression, R is identical with the compound of above-mentioned general formula (1) expression of using as raw material.
This preparation method preferably makes the compound of above-mentioned general formula (1) expression and biuret in the presence of aprotic polar solvent, under 80 ℃～300 ℃ temperature of reaction, react, via the compound of representing as the above-mentioned general formula (2) of intermediate, obtain the compound of above-mentioned general formula (3) expression, the compound of above-mentioned general formula (1) expression is 1.9～2.1 with respect to the mol ratio of biuret.
Among this preparation method,, can enumerate and 1 of above-mentioned general formula (3) expression, the identical compound of the compound that above-mentioned preparation method exemplified of 3-dialkyl group-2-imidazolone as the compound and the aprotic polar solvent of above-mentioned general formula (1) expression.
The usage quantity of aprotic polar solvent is not particularly limited, and usually, with respect to biuret 100 weight parts, its usage quantity is that 20 weight parts or 20 weight parts are above, 1000 weight parts or below 1000 weight parts.
The compound of general formula (1) expression and the usage quantity of biuret are expressed as the compound of general formula (1) expression with the mol ratio of stoichiometry: biuret=get final product at 2.0: 1.0, mol ratio is preferably 1.9: 1.0 to 2.1: 1.0.If adopt the usage quantity of above-mentioned scope, do not need to filter biuret when then purifying, so preferred.
Temperature of reaction is generally 80 ℃～300 ℃.During stepwise reaction, preferably take the method for 2 stages of branch heating, the 1st stage was more than 100 ℃ or 100 ℃, below 190 ℃ or 190 ℃, the 2nd stage was more than 180 ℃ or 180 ℃, below 300 ℃ or 300 ℃, preferred especially the 1st stage is more than 110 ℃ or 110 ℃, below 150 ℃ or 150 ℃, and the 2nd stage was more than 200 ℃ or 200 ℃, below 240 ℃ or 240 ℃.
Reaction pressure is not particularly limited, and is generally under the normal atmosphere.
The compound of general formula (1) expression and the method for biuret reaction are not particularly limited, can be implemented with any method in multiple step format and the continous way.
For example, during stepwise reaction, preferably with the compound of general formula (1) expression and biuret one-time heating to the decomposition temperature of biuret below 190 ℃ or 190 ℃, under the temperature more than 180 ℃ or 180 ℃, heat afterwards.The style that has more as the stepwise reaction method, can enumerate following method: with the mixture heating up to 110 of aprotic polar solvent and biuret ℃ or more than 110 ℃, below 150 ℃ or 150 ℃, add the compound of general formula (1) expression, making the compound of general formula (1) expression and the mol ratio of biuret is 1: 1, then be heated to more than 200 ℃ or 200 ℃, below 240 ℃ or 240 ℃, further add the compound of general formula (1) expression, making the compound of general formula (1) expression and the mol ratio of biuret is 2: 1.In addition, have aprotic polar solvent, biuret are mixed the method for reacting with the compound of all general formula (1) expressions in reaction vessel, at this moment, consider the boiling point of the compound of employed general formula (1) expression, must control reaction temperature remain on more than 180 ℃ or 180 ℃.
During successive reaction, adopt to keep in the aprotic polar solvent of heating in the temperature of reaction, add the compound of general formula (1) expression and the method for biuret continuously in reaction vessel, continuous drawing goes out reaction product.
The compound of the general formula of above-mentioned preparation method's gained (3) expression can reclaim from reaction mixture by operations such as distillations.
In addition, from other viewpoints, the present invention relates to 1 of following general formula (2) expression, 5-dialkyl group-[1,3,5] three azepans-2, the preparation method of 4-diketone.This preparation method is for making the compound and the biuret reaction of following general formula (1) expression.
In above-mentioned general formula (1) and (2), R represents that carbonatoms is 1～4 alkyl.In addition, in the compound of above-mentioned general formula (2) expression, R is identical with the compound of above-mentioned general formula (1) expression of using as raw material.
Among this preparation method,, can enumerate 1 of general formula (3) expression, the exemplary compounds described in the manufacture method of 3-dialkyl group-2-imidazolone as the compound of above-mentioned general formula (1) expression.
The compound of general formula (1) representative and the usage quantity of biuret are expressed as the compound of general formula (1) expression with the mol ratio of stoichiometry: biuret=get final product at 1.0: 1.0, mol ratio are preferably the compound of general formula (1) expression: biuret=0.8: 1.0 to 1.2: 1.0.
When making the compound of general formula (1) expression and biuret reaction, can use reaction solvent.
As reaction solvent, only otherwise with the compound reaction and the boiling point of initial feed and general formula (2) expression be to get final product more than 80 ℃ or 80 ℃, be not particularly limited.As such reaction solvent, preferably compound and the biuret by general formula (1) expression prepares 1 of general formula (3) expression, the aprotic polar solvent of enumerating as preferred solvent among the preparation method of 3-dialkyl group-2-imidazolone.
The compound of general formula (2) expression that the compound that does not separate general formula (1) expression and biuret reaction obtain and directly preparing under the situation of the compound that general formula (3) represents, because the compound that uses above-mentioned general formula (3) expression that above-mentioned reaction generates is during as aprotic polar solvent, so required and the isolating operation of solvent phase when need not to carry out to use the solvent different with it in reaction are preferably.
When using aprotic polar solvent in the compound of general formula (1) expression and the reaction of biuret, do not limit its usage quantity especially, usually with respect to biuret 100 weight parts, its usage quantity is that 20 weight parts or 20 weight parts are above, 1000 weight parts or below 1000 weight parts.
Temperature of reaction is generally 80 ℃～190 ℃.Consider from speed of response and inhibition biuret decomposition aspect, preferably this temperature range.
Reaction pressure is not particularly limited, and is generally under the normal atmosphere.
The compound of general formula (1) expression and the reaction method of biuret are not particularly limited, and can be implemented with any method in multiple step format and the continous way.
For example, during stepwise reaction, can enumerate following method: with solvent and biuret mixture heating up to 80 ℃ or more than 80 ℃, below 150 ℃ or 150 ℃, add the compound of general formula (1) expression, making the compound of general formula (1) representative and the mol ratio of biuret is 1: 1.Also make solvent, biuret and whole N, N '-dialkyl group quadrol is the method for hybrid reaction in reaction vessel together, at this moment, considers employed N, the boiling point of N '-dialkyl group quadrol, and control rationally keeps the temperature of reaction of stipulating.
During successive reaction, in the solvent of heating, keep in reaction vessel, adding N continuously in the desired response temperature, N '-dialkyl group quadrol and biuret, continuous drawing goes out reaction mixture.
The compound of the general formula that above-mentioned preparation method obtains (2) expression can utilize known method to separate from reaction mixture.For example, when separating out the compound crystal of general formula (2) expression in the reaction mixture, can be with its filtering separation.If do not separate out the compound crystal of general formula (2) expression in the reaction mixture, then remove employed solvent by distillation or add the compound do not dissolve general formula (2) expression but can with the solvent of employed solvent in the reaction, the compound crystal of general formula (2) expression is separated out etc., separate the compound of general formula (2) expression.
In addition, the compound of above-mentioned general formula (2) expression, the intermediate the when compound that can be used as general formula (1) expression and biuret reaction prepare the compound that general formula (3) represents obtains.At this moment, the compound of general formula (2) expression can not separate from reaction mixture.
Above Shuo Ming preparation method of the present invention, as 1, the preparation method of 3-dialkyl group-2-imidazolone is useful.In addition, as being used to prepare 1,1 of 3-dialkyl group-2-imidazolone, 5-dialkyl group-[1,3,5] three azepans-2, the preparation method of 4-diketone is useful.
In addition, existing by 1,5-dialkyl group-[1,3,5] three azepans-2,4-diketone and urea production 1, the method for 3-dialkyl group-2-imidazolone type is not if control preparation condition then can generate the imines by product, but it is of the present invention by making 1,5-dialkyl group-[1,3,5] three azepans-2,4-diketone and biuret reaction preparation 1, the method of 3-dialkyl group-2-imidazolone type even if do not control the compound of general formula (1) expression and the adding conditional of biuret especially, can not generate the imines by product yet.
Embodiment
Below be embodiments of the invention, but the present invention is not limited thereto.Need to prove, 1, the analysis of 3-dimethyl-2-imidazolone (below be abbreviated as DMI) is undertaken by vapor-phase chromatography (below be abbreviated as " GC ").
The condition that GC analyzes is as follows.
Chromatographic column: Thermon1000+KOH (10+3%), 3mm * 2m
Carrier gas: nitrogen
Column temperature: 170 ℃
In the 500ml glass reaction container that is equipped with agitator, prolong, thermometer, drop into 130.0g DMI and 30.9g biuret (Tokyo HuaCheng Industry Co., Ltd's product), content is warmed up to 120 ℃.Splashed into 26.5g N through 4 hours in reaction vessel, N '-dimethyl-ethylenediamine after dripping off, kept 2 hours down at 120 ℃.Reaction solution is cooled to 25 ℃, obtains the 196.5g reaction solution.Separated out 1 in the cooled reaction solution, 5-dimethyl-[1,3,5] three azepans-2, the crystallization of 4-diketone.Separate and the recovery crystallization.This crystallization is cleaned with 60ml toluene, clean after drying with the 60ml normal hexane again, obtain 32.2g 1,5-dimethyl-[1,3,5] three azepans-2,4-diketone.
1,5-dimethyl-[1,3,5] three azepans-2, the yield of 4-diketone is with respect to the N that drops into, and N '-dialkyl group quadrol is 68.2 moles of %.
Obtain 1,5-dimethyl-[1,3,5] three azepans-2, the fusing point of 4-diketone, the measurement result of 1H-NMR are consistent with the value of above-mentioned non-patent literature 2 records.
Embodiment 2
In the 500ml glass reaction container that is equipped with agitator, prolong, thermometer, drop into 257.5g DMI and 61.8g biuret (Tokyo HuaCheng Industry Co., Ltd's product), content is warmed up to 120 ℃.Splashed into 44.1g (0.5 mole) N through 2 hours in reaction vessel, N '-dimethyl-ethylenediamine after dripping off, kept 4 hours down at 120 ℃.Reaction solution is cooled to 0 ℃ kept 1 hour, obtain the 350.9g reaction solution.Separated out 1 in the cooled reaction solution, 5-dimethyl-[1,3,5] three azepans-2, the crystallization of 4-diketone.Separate and the recovery crystallization.After the cleaning of this crystallization usefulness 175.5g toluene, drying obtains 67.8g 1,5-dimethyl-[1,3,5] three azepans-2,4-diketone.
1,5-dimethyl-[1,3,5] three azepans-2, the yield of 4-diketone is with respect to the N that drops into, and N '-dialkyl group quadrol is 86.3 moles of %.
1 of gained, 5-dimethyl-[1,3,5] three azepans-2, the fusing point of 4-diketone, 1H-NMR measurement result are consistent with the value of above-mentioned non-patent literature 2 records.
In addition, with respect to the N that drops into, N '-dialkyl group quadrol, to 1,5-dimethyl-[1,3,5] three azepans-2, the total conversion rate that 4-diketone and DMI transform is 98.0 moles of %.
Embodiment 3
Drop in the 200ml glass reaction container that is equipped with agitator, prolong, thermometer that 26.0g embodiment 1 makes 1,5-dimethyl-[1,3,5] three azepans-2,4-diketone and 130.0g solvent 1,3-dipropyl-2-imidazolone is heated to 200 ℃ and kept 2 hours down synthermal.The weight that is cooled to 25 ℃ of resulting reaction solutions is 155.5g.Partial reaction liquid is carried out GC analyze, the result is that the content of DMI in the 11.4 weight % reaction solutions is 17.5g for the concentration of DMI in the reaction solution.This moment DMI yield with respect to drop into 1,5-dimethyl-[1,3,5] three azepans-2, the 4-diketone is 93.9 moles of %.
By reaction solution is distilled with the distillation tower that is equivalent to 5 layers, obtain the DMI that 15.4g purity is 99.7 weight %.
Embodiment 4
In the 500ml glass reaction container that is equipped with agitator, prolong, thermometer, drop into 159.8g DMI and 51.5g biuret (Tokyo HuaCheng Industry Co., Ltd's product), content is warmed up to 120 ℃.Splashed into 44.1gN through 2 hours in the synthermal downhill reaction container, N '-dimethyl-ethylenediamine is after dripping off, be warmed up to 200 ℃, then in reaction vessel, splashed into 44.1g N, N '-dimethyl-ethylenediamine through 2 hours 30 minutes, after dripping off, kept 1 hour down at 200 ℃ to 210 ℃.
Reaction solution is cooled to 25 ℃, obtains the 268.1g reaction solution.Partial reaction liquid is carried out GC analyze, the result is 97.5 weight % for the DMI concentration in the reaction solution.Deduct the amount of the DMI that drops in reaction vessel at first, the yield of the DMI of generation is with respect to the N that splashes into, and N '-dimethyl-ethylenediamine is 89.3 moles of %.
The gas chromatogram of reaction solution as shown in Figure 1.Do not detect 1 as can be known from this figure, 3-dimethyl-2-alkyl imidazole imine.
By reaction solution is distilled with the distillation tower that is equivalent to 5 layers, obtain the DMI that 252.0g purity is 99.7 weight %.
Comparative example 1
In the autoclave of 500ml, drop into 88g N, N '-dimethyl-ethylenediamine, 66g urea and 100g DMI.Be warming up to about 210 ℃ of temperature of reaction approximately through 30 minutes, reaction is 3 hours under this temperature.System's internal pressure is up to 15kg/cm
2About G.
After reaction was finished, content was taken out in cooling, obtains containing the slurries of white crystals, and it is filtered, and the filtrate weight that obtains is 200.1g, and DMI purity is 97.3 weight %.The yield that deducts the DMI that the amount of the DMI in the initial input autoclave tries to achieve is with respect to the N that drops into, and N '-dimethyl-ethylenediamine is 81.0 moles of %.In addition, detected 1 of 0.8 weight % in this filtrate, 3-dimethyl-2-alkyl imidazole imine.Gas chromatogram as shown in Figure 2.
Further with the filtrate distillation, the result obtains the DMI that 188g purity is 99.2 weight %, and has therefrom detected 1 of 0.7 weight %, 3-dimethyl-2-alkyl imidazole imine under the condition identical with embodiment 1.
Claims (5)
1, the preparation method of the compound of general formula (3) expression, this method is reacted the compound and the biuret of general formula (1) expression in the presence of aprotic polar solvent, via the compound of representing as the general formula (2) of intermediate, obtain the compound of general formula (3) expression
In the formula, R represents that carbonatoms is 1～4 alkyl,
In the formula, R represents that carbonatoms is 1～4 alkyl,
In the formula, R represents that carbonatoms is 1～4 alkyl.
2, the preparation method of the compound of general formula (3) expression, this method makes the compound of general formula (1) expression and biuret in the presence of aprotic polar solvent, under 80 ℃～300 ℃ temperature of reaction, react, via the compound of representing as the general formula (2) of intermediate, obtain the compound of general formula (3) expression, the compound of described general formula (1) expression is 1.9～2.1 with respect to the mol ratio of described biuret
In the formula, R represents that carbonatoms is 1～4 alkyl,
In the formula, R represents that carbonatoms is 1～4 alkyl,
In the formula, R represents that carbonatoms is 1～4 alkyl.
3, the preparation method of the compound of general formula (3) expression, this method makes the compound of general formula (1) expression and biuret in the presence of aprotic polar solvent, under 80 ℃～300 ℃ temperature of reaction, react, obtain the compound of general formula (3) expression, the compound of described general formula (1) expression is 1.9～2.1 with respect to the mol ratio of described biuret
In the formula, R represents that carbonatoms is 1～4 alkyl,
In the formula, R represents that carbonatoms is 1～4 alkyl.
4, each preparation method who puts down in writing in the claim 1～3, wherein, described aprotic polar solvent is the compound of general formula (3) expression.
5, the preparation method of the compound of general formula (2) expression, this method is reacted the compound and the biuret of general formula (1) expression under 80 ℃～190 ℃ temperature of reaction, obtain the compound of general formula (2) expression, the compound of described general formula (1) expression is 0.8～1.2 with respect to the mol ratio of described biuret
In the formula, R represents that carbonatoms is 1～4 alkyl,
In the formula, R represents that carbonatoms is 1～4 alkyl.
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